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Energy- and resource-efficient electrocatalytic water splitting is of paramount importance to enable sustainable hydrogen production. The best bulk catalyst for the hydrogen evolution reaction (HER), i.e., platinum, is one of the scarcest elements on Earth. The use of raw material for HER can be dramatically reduced by utilizing nanoclusters. In addition, nanoalloying can further improve the performance of these nanoclusters. In this paper, we present results for HER on nanometer-sized ligand-free AuPt nanoclusters grafted on carbon nanotubes. These results demonstrate excellent monodispersity and a significant reduction of the overpotential for the electrocatalytic HER. We utilize atomistic machine learning techniques to elucidate the atomic-scale origin of the synergistic effect between Pt and Au. We show that the presence of surface Au atoms, known to be poor HER catalysts, in a Pt(core)/AuPt(shell) nanocluster structure, drives an anomalous enhancement of the inherently high catalytic activity of Pt atoms.

Inspired by emergent behaviors of living matter, there is increasing interest in developing approaches to create dynamic patterns and structures in synthetic materials with controllable complexity to enable functionalities that are not possible in thermodynamic equilibrium. Here we show that electrophoretically driven and maintained non-equilibrium gradients of magnetic nanoparticles in non-polar solvent can undergo electrokinetic instabilities (EKI), leading to various electrically controllable spatiotemporally patterned states. These electrokinetic instabilities and patterns can be tuned with a magnetic field via magnetostatic energy reduction mechanism to both increase and decrease the pattern complexity. We reflect the experimental observations on the theoretical electrokinetic and magnetostatic arguments. We further show that small amounts of polar water in the otherwise non-polar system are critical enablers for the electrophoretic mobility of the nanoparticles. Since functionalities of magnetic nanoparticles are widely tunable, we foresee that the combination of dissipative electrokinetic driving and magnetic energy reduction can lead to novel functional dissipative materials.

Materials with continuous dissipation can exhibit responses and functionalities that are not possible in thermodynamic equilibrium. While this concept is well-known, a major challenge has been the implementation: how to rationally design materials with functional non-equilibrium states and quantify the dissipation? Here we address these questions for the widely used colloidal nanoparticles that convey several functionalities. We propose that useful non-equilibrium states can be realised by creating and maintaining steady-state nanoparticle concentration gradients by continuous injection and dissipation of energy. We experimentally demonstrate this with superparamagnetic iron oxide nanoparticles that in thermodynamic equilibrium form a homogeneous functional fluid with a strong magnetic response (a ferrofluid). To create non-equilibrium functionalities, we charge the nanoparticles with anionic charge control agents to create electroferrofluids where nanoparticles act as charge carriers that can be driven with electric fields and current to non-homogeneous dissipative steady-states. The dissipative steady-states exhibit voltage-controlled magnetic properties and emergent diffuse interfaces. The diffuse interfaces respond strongly to external magnetic fields, leading to dissipative patterns that are not possible in the equilibrium state. We identify the closest non-dissipative analogues of these dissipative patterns, discuss the differences, and highlight how pattern formation in electroferrofluids is linked to dissipation that can be directly quantified. Beyond electrically controlled ferrofluids and patterns, we foresee that the concept can be generalized to other functional nanoparticles to create various scientifically and technologically relevant non-equilibrium states with optical, electrical, catalytic, and mechanical responses that are not possible in thermodynamic equilibrium.

We investigate the electromagnetic properties of assemblies of nanoscale $\epsilon$-cobalt crystals with size range between 5 nm to 35 nm, embedded in a polystyrene (PS) matrix, at microwave (1-12 GHz) frequencies. We investigate the samples by transmission electron microscopy (TEM) imaging, demonstrating that the particles aggregate and form chains and clusters. By using a broadband coaxial-line method, we extract the magnetic permeability in the frequency range from 1 to 12 GHz, and we study the shift of the ferromagnetic resonance with respect to an externally applied magnetic field. We find that the zero-magnetic field ferromagnetic resonant peak shifts towards higher frequencies at finite magnetic fields, and the magnitude of complex permeability is reduced. At fields larger than 2.5 kOe the resonant frequency changes linearly with the applied magnetic field, demonstrating the transition to a state in which the nanoparticles become dynamically decoupled. In this regime, the particles inside clusters can be treated as non-interacting, and the peak position can be predicted from Kittel's ferromagnetic resonance theory for non-interacting uniaxial spherical particles combined with the Landau-Lifshitz-Gilbert (LLG) equation. In contrast, at low magnetic fields this magnetic order breaks down and the resonant frequency in zero magnetic field reaches a saturation value reflecting the interparticle interactions as resulting from aggregation. Our results show that the electromagnetic properties of these composite materials can be tuned by external magnetic fields and by changes in the aggregation structure., Comment: 14 pages, 13 figures